Synthesis of unsaturated hydrocarbons



United States Patent 3,551,463 SYNTHESIS OF UNSATURATED HYDROCARBQNSNorbert F. Cywinski, Bartlesville, kla., assignor to Phillips PetroleumCompany, a corporation of Delaware No Drawing. Filed May 14, 1964, Ser.No. 367,581 Int. Cl. 'C07c 67/00 US. Cl. 260-410 9 Claims ABSTRACT OFTHE DISCLOSURE Non-conjugated diolefins, unsaturated aldehydes andunsaturated ketones are produced by reacting acetylenic hydrocarbonswith cyclic or acyclic monoolefins, a primary or secondary allylicalcohol or an ester of a primary or a secondary allylic alcohol.

This invention relates to a method of preparing unsaturated hydrocarbonsand the product thereof. In one of its aspects, this invention relatesto the production of unsaturated organic compounds by reacting anacetylene and an unsaturated organic compound. In another of itsaspects, this invention relates to the production of carbonyl compoundshaving unsaturation gamma to the carbonyl group by reaction of anacetylene and an allyl alcohol or an allylic ester at a suitablyelevated temperature and pressure. In another aspect, this inventionrelates to the production of non-conjugated dienes by reaction of anacetylene and an olefin at a suitably elevated temperature and pressure.In another aspect, this invention relates to a reaction wherebyunsaturated aldehydes or ketones having a double bond gamma to thecarbonyl group are produced. In another aspect, this invention relatesto a process whereby non-conjugated diolefins are produced. In anotheraspect, this invention relates to certain novel diolefins produced bythe method abovedescribed.

The synthesis of aldehydes or ketones having unsaturation alpha to thecarbonyl group is readily effected by such processes as chlorination atthe alpha position, followed by dehydrochlorination. It is verydifiicult to obtain aldehydes and ketones having unsaturation fartherremoved from the carbonyl group than the alpha position. Non-conjugateddiolefins are also very difficult to synthesize since they readilyisomerize to the conjugated state.

Since aldehydes and ketones are well known intermediates for chemicalsynthesis and since non-conjugated diolefins are also of interest asintermediates for chemical synthesis as well as being of interest astermonomers for use in ethylene-propylene rubber, it is highly desirableto find a practical method of producing these materials.

It is known to react olefins and acetylene at super ambient temperaturesand pressures to produce conjugated diolefins. It is also known, Sauerand Sausen, J. Organic Chemistry, 27 2730 (1962), to react an olefinwith an electronegatively substituted acetylene at super ambienttemperatures and autogenous pressures.

It has now been found that unsaturated aldehydes, unsaturated ketonesand unsaturated hydrocarbons as herein described can be produced byreacting a primary or secondary allylic alcohol or ester thereof or anolefin with an acetylene at a suitably elevated temperature andpressure.

Accordingly, it is an object of this invention to provide a practicalmethod for producing unsaturated hydrocarbons. Another object of thisinvention is to produce non-conjugated dienes. Yet another object ofthis invention is to produce aldehydes and ketones having unsaturationgamma to the carbonyl group.

Other aspects, objects and the several advantages of the invention areapparent from a study of this disclosure and the appended claims.

The broad concept of this invention is represented by the followinggeneral equation:

(3) where R is either hydrogen or lower alkyl and the total number ofcarbon atoms in R is not greater than three; where R R R and R arehydrogen or hydrocarbon radicals selected from the group consisting ofsaturated aliphatic, saturated cycloaliphatic, and aromatic radicals andcombinations thereof, and are not necessarily the same, and the numberof carbon atoms in each radical does not exceed about 12; where R and Rcan be joined to form a 5- or 6-membered cyclic compound when Z ishydrogen; where the total number of carbon atoms present in (2) is notmore than 24; and where Z is H,

where R is a radical as defined above for R R The general formula statedabove is clearly applicable to at least one material selected from thegroup consisting of cyclic and acyclic olefins, allylic alcohols andallylic esters. Consideration of the general reaction as illustrated byEquation I indicates that the portion of reactant (2) represented by Zhas little if any influence on the initial reaction, and therefore, thatZ can optionally be any nonreacting non-directing radical, such asamine, amide, substituted amine, and the like.

More specifically, according to this invention, unsaturated aldehydes orketones having a double bond gamma to the carbonyl group can besynthesized by the addition of an acetylene to a primary or secondaryallylic alcohol, accompanied 'by allylic rearrangement of the alcohol tothe enol form of the aldehyde or ketone, and followed by rearrangementto the aldehyde or ketone or by the addition of an acetylene to theester of a primary or secondary allyl alcohol followed by hydrolysis ofthe reaction product and rearrangement of the hydrolyzed reactionproduct to said aldehyde or ketone. The general equations for thereaction of an acetylene with the allylic alcohol or ester are:

Rearrangement H 1 R3 R4 R5 (Ill) Rearrangement The reaction is highlyselective and the desired addition product is usually isolated bydistillation. If an ester is used as a reactant, the product isolationcan be elTected either before or after hydrolysis of the reactionproduct of the acetylene and the ester. Major side reactions are thermaldecomposition of the acetylene to produce carbon, and production ofhigher molecular weight compounds. These side reactions can be minimizedby proper control of the ratio of reactants and the reaction conditions.

Also in accordance with this invention and as illustrated in Equation I,with Z equal to hydrogen or a hydrocarbon radical, non-conjugateddienes, for example, 1,4- diolefins, can be synthesized by the allylicaddition of cyclic or acyclic olefins and acetylenes at an elevatedtemperature and an elevated pressure. The process of this inventionrequires no catalysts or initiators. The addition reaction is carriedout simply by heating the reactants at a temperature of about 200 toabout 600 C., preferably about 300 to about 400 C., at a pressure ofabout 250 to about 50,000 p.s.i.g., preferably about 500 to about 25,000p.s.i.g., still more preferably about 1,000 to about 5,000 p.s.i.g., andfor a contact time of about 1 second to about 120 minutes, preferablyabout 1 to about 60 minutes, more preferably about 6 to about 40minutes. The reaction is conveniently carried out by dissolving theacetylene in the second reactant and pumping the mixture through areactor heated to the desired temperature. The reaction can be carriedout as a batch, a continuous or a semi-continuous process. In acontinuous process, the indicated contact times correspond to liquidhourly space velocities (LHSV) of about 0.5 to about 3600, preferablyabout 1 to about 60, more preferably about 1.5 to about 10 volumes ofliquid per volume reactor space per hour.

The acetylene will usually comprise from 1 to 30, preferably S to 15,weight percent of the total reactants.

The acetylenic compounds or materials that can be employed according tothis invention are the l-acetylenes containing from 2 to 5 carbon atomsand include acetylene, l-propyne, l-butyne, l-pentyne, and3-methyl-lbutyne and mixtures thereof. The usual precautions forhandling acetylene under pressure should be observed. Explosions can beprevented in handling acetylene under pressure by dilution with othergases (nitrogen, methane, etc.), operating with limited free space inthe lines and vessels in which acetylene is under pressure, and othermeans known in the art for handling acetylene.

The alcohols that can be employed according to this invention includeprimary and secondary alcohols containing from 3-24 carbon atoms, forexample:

propen-1-ol-3 (allyl alcohol),

2-methylpenten-2-ol-4,

hexen-4-ol-6,

3,3,7-trimethyl-4-ethyl-5-cycloheXylocten-4-ol-6,

2-phenyl-3-methyl-4-( 1-naphthyl)hexen-3 -ol-53-isobutyl-6-cyclohexyl-8-phenylocten-6-ol-8,

5-(2,5-dimethyl-cyclohexyl) -7- (4-methylphenyl)hepten-2-methylpenten-2-ol-4,

4-isobutyl-5-cyclohexylhexen-4-ol-6,

2-methyl-4-ethyl-5-phenylnonen-4-ol-6, and the like.

The esters that can be employed according to this invention includeesters containing from 4-24 carbon atoms, for example: the formic acidester of propen-l-ol- 3, the acetic acid ester of buten-1-ol-3, thecyclobutanecarboxylic acid ester of 3-benzyl-4-ethylocten-3-ol-5, thelauric acid ester of 2-methyl-4-cyclohexylpenten-3-0l-5, the benzoicacid ester of 2-methylhepten-4-ol-6, the cyclohexaneacetic acid ester of2-methyl-5-cyclopentylpenten- 2-ol-4, the Z-naphthoic acid ester of8-methylenenonanol- 9, the garnma-cyclopentaneoctanoic acid ester ofl-cyclohexyl-2,3-dimethylpropen-l-ol-3, the beta-3-ethylbenzenebutyricacid ester of 6-n-pentylhepten-5-ol-7, the 4-nbutylcyclohexanecarboxylicacid ester of decen-3-ol-5, and the like.

The olefins that can be employed according to this invention includecyclic and acyclic monoolefins containing from 3-24 carbon atoms, forexample: propylene, isobutylene, butene-1, cis-butene-Z, trans-butene-Z,pentene-2, Z-methylbutene-l, 3-methylbutene-1, Z-methylbutene 2,cyclohexene, 4 methylpentene 1, trans 4- methylpentene 2, 2,3dimethylbutene-l, 2,3-dimethylbutene-2, 2,4,4-trimethylpentene-l,3-cyclohexyl-4-isopropylnonene-3, 2-cyclopentyl-5-phenylpentene-2,3-(2-naphthyl -4- 3-ethylcyclohexyl hexene-31,3-di-n-butylcyclopentene-l, 2-phenylcyclohexene-l,4-(3,4-dimethylcyclohexyl)cyclohexene-1, and the like.

The aldehydes produced by this invention include: penten-l-al,4-vinylhexanal, 8-allylnonanal, 5-vinyl-6-npentylheptanal, 2methyl-3-vinyl-4-cyclohexylpentanal, and the like.

The ketones produced by this invention include: 2,2,4-trimethylhexen-l-one-S, 3,3,7-trimethyl-4-ethyl-4-vinyl-5-cyclohexyloctanone-6, 3,3-dimethylhexen-l-one-S, 3-isobutyl6-vinyl-6-cyclohexyl-S-phenyloctanone-8, hexen-lone-5, and the like.

The dienes produced by this invention include cyclic and acyclicdiolefins containing from 3-24 carbon atoms, for example:

2-methyl-l,4-pentadicne, cis-l,4-hexadiene, trans-1,4-hexadiene,3-methyl-l,4-pentadiene, 3-methyl-1,4-hexadiene, 3-ethyl-l,4-pentadiene,cis-4-methyl-l,4-hexadiene, trans-4-methyl-1,4-hexadiene,2-ethyl-1,4-pentadiene, 5-methyl-1,4-hexadiene,2,3-dimethyl-1,4-pentadiene, 3,3-dimethyl-1,4-pentadiene,3-vinylcyclohexene, 6-methyl-1,4-heptadiene,

3,5 -dimethyll ,4-hexadiene, 3-isopropyl-1,4-pentadiene,

4,5 -dimethyl-1,4-hexadiene, 2-isopropyl-1,4-pentadiene,2,3,3-trimethyl-1,4-pentadiene, 2-neopentyl-1,4-pentadiene,4,6,6-trimethyl-l,4-heptadiene, 2,6,6-trimethyl-1,4-heptadiene,2-tert-butyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, and the like.

The products listed above are prepared from certain of the alcohols,esters, and olefins listed previously by reaction with acetylene. If ahigher acetylene is used, products such as hepten-4-al,6-methylhepten-4-al, 0cten-5- one-2, 4-methyl-2,5-octadiene,1-phenyl-4-cyclopentyl-2,5- octadiene, and the like, are obtained.

It should be noted that any one of the acetylenes encompassed by theabove disclosure can be reacted with any one of the alcohols, esters andolefins also encom passed within the above disclosure to produce thematerials contemplated by this invention. For example, the sameacetylenic material can be used to react with butene- 1 to produce1,4-hexadiene, to react with allyl alcohol to produce penten-l-al, andto react with an acetic acid ester of buten-l-ol-3 to yieldhexen-l-one-S. Mixtures of the above named reactants can also beemployed in the practice of this invention.

EXAMPLE I A one-liter bomb containing 473 ml. of allyl alcohol wascooled to 0 C. and the alcohol was saturated with acetylene at apressure of 60 p.s.i.a. The resulting solution was pumped through ametal'reactor heated to 350 C. at 3.5 LHSV and 2,500 p.s.i.g'. Unreactedacetylene was vented from the product and the product was distilled. A 6percent yield of 4-penten-1-al based on the alcohol charged wasobtained.

alcohol and (2) an ester of a primary or secondary allylic alcohol, saidcompound being represented by the formula R R R EXAMPLE 11 o=c-hz 5 Areaction was conducted in the same manner and unit 1'1 gril E: gge i z zi b t i g z g where R R R and R are hydrogen or hydrocarbon m f f 11 3th i) g d e radicals selected from the group consisting of saturated f 33 1: 6 T 5 2 0 31 was f aliphatic, saturated cycloaliphatic, andaromatic radicals yze tam exen' good V was obtamfid- 10 and combinationsthereof, and are not necessarily the From Examples and It F be seen thata Practlcal same, and the number of carbon atoms in each radical methodof producing the deslred unsaturated aldehydes does not exceed aboutWhere Z is and ketones is presented by this invention.

EX MPLE III H A 15 OH or -OCRB In thls f i acetylene w P f Into a feedwhere R is a radical as defined above for R R and tank conta ning theolefin to glve the lndrcated acetylene Where the total number of carbonatoms present in (1) is corlcentl'atlQna f the mlxture was P m ug a notmore than 24, at a temperature ranging from about stainless-steel pipereactor under the indicated conditions 2004000 C and a pressure rangingfrom about 1 to glve the mdlcflted Yleld of P 50,000 p.s.i.g., therebyforming a product represented by Yield of 1,4-d1olefin was determinedelther by dlstlllathe formula tion or gas chromatography analysis of theproduct. Identification of the 1,4-diolefin was done by infrared or NMRf (nuclear magnetic resonance) spectroscopy. H--C=OOC-C=O The data forthis example are shown in Table I.

TABLE I OzHz Total i l Temp Pressure 1n Feed Hyc wt. percent p.s.1.g.wt. percent Olefin used LHSV Diolefin made of product 355 2, 500 10.6Isobutylene 2. 4 5 s 1, s00 11. 0 d 1. 3' 0 355 2, 500 14. 0 2. 4' 4 3502, 500 8.6 1. 3' 4 338 2,500 7.4 1. 217 358 2,500 8.5 Butene-l 1.61,4-hexadiene:cis 1.2 1,4-hexadiene: trans 1. 6 358 2,500 8.5cis-Butene-2 1.0 3-m th 1-14 d 358 2,500 8.5 trans-Butene-Z 1.5 uhoijflfi iiiffii. 350 2,500 10 Pentene-2 3.5 gfiffifi tggga gg4methyl-1,4-hexadiene: is- 2:5 355 2,500 10 2methy1butene 1 4.2{4-methyl-L4-hexadiene: trans 2.5 2-ethyl-l,4- entadiene 3.0 350 2,50010 3-methylbutene-1 3.0 fi-methyl-lfi-hexadienen 3.05-methyl-1,4-hexadiene 1. 2 360 2,500 10 2-methylb ene-2 3.55,3-gimethyI-IA-pentadiene 6.0 ,3- imethyl-lA- entadiene 0.6 355 2,50010 cyclohexene 4.2 avinyle clohexege 3.6 360 2,500 10 4-rnethy1pentene-13.5 6-methyl-l,4heptadien e 5.0 350 2, 500 10 trans-4 methylpentene-23.5 {gjgggzggfi'iiggggf 355 2,500 10 2,3-dimethylbutene-1 3.5 fggfiifgff fi fgfgx- 355 2,500 10 2,3-dimethylbutene-2 4.5 {'g ff g;ff;:$ r'ztr t trr rr-- 350 2,500 10 2,4,4trimethylpentene-1 3.0 t m W 76D t 2,6,fi'trimethyl-l,4heptad1ene O or 2-tert-B utyl-l,4-hexadiene BThese are approximate figures because of the presence of acetylene inthe olefin feed. b It was not possible to decide between these two withthe NMR and infrared spectroscopic data available.

From Example III, it can be seen that cyclic and acyclic non-conjugateddiolefins are readily prepared by this invention.

Reasonable variation and modification are possible within the scope ofthe foregoing disclosure, and the appended claims to the invention, theessence of which is that there have been provided a method forsynthesizing an unsaturated aldehyde or ketone having a double bondgamma to the carbonyl group by the addition of an acetylene to a primaryor secondary allylic alcohol or ester thereof followed by hydrolysis,and a method for producing a nonconjugated diolefin by the allylicaddition of cyclic or acyclic olefins and acetylenes, all of whichreactions are conducted at a suitably elevated temperature and anelevated pressure.

I claim:

1. The method comprising reacting a l-alkyne having from 2 to 5 carbonatoms with a compound selected from the group consisting of, -(1) aprimary or secondary allylic where R R R and R are hydrogen orhydrocarbon radicals selected from the group consisting of saturatedaliphatic, saturated cycloaliphatic, and aromatic radicals 7 andcombinations thereof, and are not necessarily the same, and the numberof carbon atoms in each radical does not exceed about 12; said compoundcontaining from 3 to 24 carbon atoms, at a temperature ranging fromabout ZOO-600 C. and a pressure ranging from about 1,00050,000 p.s.i.g.,thereby forming a product represented by the formula B3 II where R iseither hydrogen or lower alkyl and the total number of carbon atoms in Ris not greater than three, and where R R R and R are as defined above.

3. A method of preparing an organic compound comprising reacting andlI-CEC-Rr wherein R is either hydrogen or lower alkyl and the totalnumber of carbon atoms in R is not greater than three; where R R R and Rare hydrogen or hydrocarbon radicals selected from the group consistingof saturated aliphatic, saturated cycloaliphatic, and aromatic radicalsand combinations thereof, and are not necessarily the same, and thenumber of carbon atoms in each radical does not exceed about 12; where Ris a radical as defined above for R R at a temperature ranging fromabout 200600 C. and a pressure ranging from about 1,000- 50,000p.s.i.g., to produce 11 R1 It, 1( 0 11 U tl :d t & 1t.

where R R R R and R are as defined above.

4. A method according to claim 3 wherein said temperature is in therange of about 300400 C. and said pressure is in the range of about1000-5000 p.s.i.g.

5. The method according to claim 1 wherein said 1- alkyne is reactedwith said primary or secondary allylic alcohol.

6. The method according to claim 1 wherein said 1- alkyne is reactedwith said ester of a primary or secondary allylic alcohol.

8 7. A method of preparing an organic compound comprising reacting and8. A method according to claim 7 wherein (2) is allyl alcohol and saidtemperature is in the range of about 300-400 C. and said pressure is inthe range of about 1,0005,000 p.s.i.g.

9. A method according to claim 3 wherein (2) is the acetic acid ester ofbutene-1-ol-3 and said temperature is in the range of about BOO-400 C.and said pressure is in the range of about 1,0005,000 p.s.i.g.

References Cited UNITED STATES PATENTS 2,875,240 2/1959 Braunwarth etal. 260-638X 2,197,257 4/1940 Burk 260-680 1,436,819 11/1922 Plauson260680 LEON ZITVER, Primary Examiner R. H. LILES, Assistant Examiner US.Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF cwmcnm Patent. No. 51,463Norbert F. Cyu'inski Dated Dec. 29, 19

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 8, line 7, the end of the formula, "-NH" should read -0H Signedand sealed this 23rd day of March 1971 (SEAL) Attest:

WILLIAM E. SCHUY'LER, JR.

EDWARD ILFLETCHERJR. Attesting Officer Commissioner of Patents

